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US2761852A - Basic polyureas - Google Patents

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US2761852A
US2761852A US238403A US23840351A US2761852A US 2761852 A US2761852 A US 2761852A US 238403 A US238403 A US 238403A US 23840351 A US23840351 A US 23840351A US 2761852 A US2761852 A US 2761852A
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basic
polyurea
ethanol
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Lehmann Wolfgang
Rinke Heinrich
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Bayer AG
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Bayer AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders

Definitions

  • the present invention relates to basic polymers and more particularly to basic polycarbamides and polyurethanes.
  • polycarbamides polyureas
  • polyurethanes by the reaction of diprimary diamines with diisocyanates or glycol-bis-chlorocarbonates, the reaction could not be applied to diamines having in addition to their primary amino groups one or several secondary amino groups, since both the diisocyanates and the bis-chlorocarbonates react also with the secondary amino groups, thus excluding the possibility of obtaining linear highly polymeric products.
  • Another object of the invention is to provide a process by which these disadvantages can be avoided. Another object is to provide novel basic polycarbamides or polyurethanes having valuable properties for many industrial applications and especially for textile printing. Other objects will become apparent as the following specification proceeds.
  • Amines dissolve in alcohols with evolution of heat. It is assumed that the molecules of the alcohol are added to the amine with the formation of oxonium compounds of the following kind.
  • diethylene triamine adds mols of methanol or eight mols of ethanol.
  • the invention is based on the discovery that addition products of diamines with alcohols, readily obtainable by dissolving a diamine in alcohol, react much more slowly with diisocyanates or bis-chlorocarbonates of glycols than the free diamines.
  • the speed of reaction of these addition products with the diisocyanates or bis-chlorocarbonates is, however, substantially higher than that of the alcohol, so that side reactions, which result in stopping the growth of the chains and in cross-linking are not observed.
  • the addition of the alcohol to the secondary amino group is so stable, that only the primary amino groups react with the formation of highly polymeric compounds.
  • the process of this invention easily yields basic poly- CgHs ureas or polyurethanes with molecular Weights, which ice ture remains moderate in spite of the strongly exothermic character of the reaction.
  • alcohols those are preferred in which the reactants are soluble, for instance the lower aliphatic alcohols like ethanol.
  • a part of the alcohol may be replaced by other solvents, such as chlorobenzene, benzene, tetrahydrofurane etc.
  • the process may easily be carried out continuously. It is also possible to employ the reaction for enhancing the chain length of basic polyamides or polyoxamides of low degree of polymerisation by reacting the same in alcoholic solution with diisocyanates or glycol-bis-chlorocarbonates.
  • the basic polymers which are soluble in dilute acetic acid may be cross-linked with diethyloxalate, formaldehyde or compounds yielding formaldehyde upon decomposition, diketenes, diisocyanates, hexahydro-l.3.5-triacrylyl-s-triazine, by which reaction they are rendered insoluble.
  • suitable selection of the kind and amount of the cross-linking agent products of a varying degree of cross linking which are more or less capable of swelling, may be obtained.
  • the products of the invention are suited to a number of industrial applications.
  • they may be used for rendering textile fibers dyeable with acid dyestufis or water repellent, or they may be employed as binders in pigment printing.
  • they are preferably used in the form of their salts in aqueous solution.
  • the solution of the basic polymer in a dilute acid, for instance, acetic acid is mixed with a pigment paste containing a cross-linking agent and then brought to the necessary thickness by the addition of water and the usual thickener-s. It is possible to adjust the production of the polymers in such a manner that the salts of the polymer yield so viscous an aqueous solution that the addition of a thickener can be omitted.
  • Mixtures of this kind constitute stable printing pastes of favorable consistency.
  • the paste is printed on a surface in the usual manner.
  • the printed surface is thereupon heated.
  • Prints are obtained which excel by their depth and brilliancy of color, good fastness to rubbing during washing and a very good fastness to boiling in soda. and to light.
  • the pigmented basic polymers may be employed for pigment printing after dissolving in aqueous acetic acid, adding the cross-linking agent and other suitable auxiliaries. Prints obtained from such polymers possess an especially good fastness to rubbing.
  • Example 1 wherein 'q is the relative viscosity and c is the concentration in grams per liter.
  • the polymer is easily'soluble in ethanol and dilute acetic acid and may be cross-linked with cross-ljnking agents, for instance ethyloxalate'and/or cliisocyanates.
  • Example 2 I A solution of 167 grams .of -hexamethylene'-.diis'oc y a.
  • Example 4 The alcoholic solutions of 103 grams of diethylenetriamine, 79 grams of pyridine in 4 liters of crude ethanol and 215 grams of tetramethyleneglycol-bis-chlorocarbonate of the formula Cl.CO.O.(CI-I2)4.O.CO.Cl
  • a basic polyurethane separates as a hydrochloride; after two hours it is sucked ofi, washed with ethanol and dried at 90100 C.
  • the hydrochloride of the polymer shows a viscosity number of 48 10 in concentrated sulfuric acid and a melting point of 202-204 C.
  • the basic polyurethane may be liberated from the aqueous solution of the hydrochloride by the addition of alkali. It may be cross-linked with the usual crosslinking agents as such or after spinning and cold-drawing and may thus be rendered insoluble.
  • Example 5 A solution in alcohol of 243 grams of 'hexamethylene- V glycol-bis-chloro-carbonate is dropped within 15 minutes into a cooled solution of 103. grams of diethylenetriamine, 79 grams of pyridine and 5 liters of ethanol. When about 80 per cent of the chlorocarbonate have been dropped in,
  • Example 6 The solution of 0.9 mols of diethyloxalate (131.3 grams in one liter of ethanol) is added to a solution of 1 mol of spermin (202 grams in 5 liters of ethanol). After minutes a freshly prepared solution of 0.1 mol hexamethylenediisocyanate (16.8 grams) in 100 ccs. of alcohol is added. The polymer begins to separate after 5 hours. 24 hours after the addition of the diisocyanate solution the residue is sucked ofif, washed with alcohol and dried in vacuo at 80 C. The yield amounts to 116 grams. The melting point of the polymer is 146148 C., the viscosity number z 45 l0- The polymer dissolves easily in dilute acetic acid.
  • Example 7 A The solution of 0.1 mol'of hexamethylenediisocyanate (16.8'grams) in 100 ccs. of ethanol are added toa solution of l mol (202 grams) of spermin in 5 liters of ethanol. After 45 minutes a solution of 0.9 mol of diethyloxalate (131 grams) in one liter of ethanol is added. Fivebours. late'rthepolymer. begins tosepariate. It is sucked off after storing for a day, washed with ethanol and dried in vacuo at -90 C. The yield amounts to grams, the melting point is 154-156 C., the viscosity number Z1) is 62 10- 'polyurea amounts to 36.5 kg, of dried polyurea 16.4
  • the vviscosity number is 400x 10 the melting point 208-2l0 C.
  • the filtrate, which contains low molecular weight compounds may be employed without intermediate distillation as a solvent for the next batches. The yield can thus be increased to 99 per cent of the theoretical.
  • the basic polyurea is easily soluble in dilute acetic, acid and .yields a clear, viscous solution.
  • a 10 per cent solution of its acetate shows a viscosity of 620 centipoise at 25 C.
  • the basic polyurea can be employed for pigment printing in the following manner:
  • the mixture described above yields a stable printing paste of good consistence which 'may easily be rinsed with water from the printing rollers or film printing matrices.
  • the printing paste is printed in the usual manner on cotton fabrics or rayon staple fabrics. For aftertreatment the print is predried at 40,70 C.; subsequently prints on cotton are heated to 100-110 C., prints on rayon staple or rayon are heated to 130 C.
  • the prints on cotton, rayon staple or rayon have good depth and brilliancy of color, very good fastness to rubbing during washing, very good fastness to boiling in soda and to light.
  • Example 9 cooled freshly prepared solution of 171.4 grams 1.02 mol per cent) of hexamethylenediisocyanate in 2.00 ccs. of ethanol is'introduced inside 10 minutes into a cooled solution of 5.05 grams of spermin (2.5 mol per cent), 141.2 grams of 'yl'y-diaminopropylmethylamine (97.5 mol per cent) in two liters of ethanol. After 7 hours the polymer begins to separate; The mixture is stirred for another hour and the basic polyurea precip itated is sucked off, dried for some hours in vacuo at 65-- 70 C. in order to remove the solvent. The yield amounts to 301 grams or 95 per cent or" the theoretical.
  • the melting point is 21l2l3 C.
  • the viscosity number Z11 is 442 10
  • the polyurea thus obtained may be used as a pigment binder in padding according to the following formula:
  • the basic polyurea thus obtained may be employed as a binder in pigment printing according to the following formula:
  • Example 11 The mixture of 135 parts by weight of powdered Hansa Yellow 10 G, 5.06 parts by weight of diethylenetriamine, 135 parts by weight of 'y-y-diaminopropylmethylamine and two liters of ethanol is stirred for two hours at room temperature. The mixture is cooled to -l C. and a freshly prepared cooled solution of 168 parts by weight of hexamethylenediisocyanate in 200 parts by weight of ethanol is dropped in within ten minutes. After stirring for another hour the polymer is sucked ofi and dried for some hours in vacuo at 70 C.
  • a basic polyurea containing recurring NHCONH CH2) aNH CH2) zNHCONH CH2) 6 groups and being soluble in dilute aqueous acids.
  • a basic polyurea containing recurring groups and being soluble in dilute aqueous acids.
  • a polyurea obtained by reacting in a monohydric lower aliphatic alcohol, a mixture of diethylene triamine and gamma, gamma-diaminopropylmethylamine with about equimolecular proportions of hexamethylene diisocyanate.
  • An aqueous textile printing paste comprising a pigment and as a binder the acetic acid salt of the polymer of claim 9.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Polyurethanes Or Polyureas (AREA)

Description

BASH; romzunnas Wolfgang iiehrnann, Leverlmsen-Bayerwerk, and Heinrich Rinke, Leverkusen, Germany, assignors to Far-benfabrllsen Bayer Alrtiengesellschaft, Leverkusen, Germany, a corporation oi Germany No Drawing. Application .luly 24, 1951, Serial No. 238,403
Claims priority, application Germany July 24, 1950 11 Claims. (Cl. 26029.2)
The present invention relates to basic polymers and more particularly to basic polycarbamides and polyurethanes.
Although it was known to produce polycarbamides (polyureas) or polyurethanes by the reaction of diprimary diamines with diisocyanates or glycol-bis-chlorocarbonates, the reaction could not be applied to diamines having in addition to their primary amino groups one or several secondary amino groups, since both the diisocyanates and the bis-chlorocarbonates react also with the secondary amino groups, thus excluding the possibility of obtaining linear highly polymeric products.
It is an object of the invention to provide a process by which these disadvantages can be avoided. Another object is to provide novel basic polycarbamides or polyurethanes having valuable properties for many industrial applications and especially for textile printing. Other objects will become apparent as the following specification proceeds.
We have found, that highly molecular linear basic polyureas and polyurethanes are obtained by reacting in the presence of a lower aliphatic alcohol a diprimary aliphatic diamine containing in the carbon chain one or several secondary amino groups with a diisocyanate or a glycol-bis-chlorocarbonate.
Amines dissolve in alcohols with evolution of heat. It is assumed that the molecules of the alcohol are added to the amine with the formation of oxonium compounds of the following kind.
For instance, it could be ascertained that diethylene triamine adds mols of methanol or eight mols of ethanol.
The invention is based on the discovery that addition products of diamines with alcohols, readily obtainable by dissolving a diamine in alcohol, react much more slowly with diisocyanates or bis-chlorocarbonates of glycols than the free diamines. The speed of reaction of these addition products with the diisocyanates or bis-chlorocarbonates is, however, substantially higher than that of the alcohol, so that side reactions, which result in stopping the growth of the chains and in cross-linking are not observed. Further it has been found, that the addition of the alcohol to the secondary amino group is so stable, that only the primary amino groups react with the formation of highly polymeric compounds.
The process of this invention easily yields basic poly- CgHs ureas or polyurethanes with molecular Weights, which ice ture remains moderate in spite of the strongly exothermic character of the reaction. As alcohols those are preferred in which the reactants are soluble, for instance the lower aliphatic alcohols like ethanol. A part of the alcohol may be replaced by other solvents, such as chlorobenzene, benzene, tetrahydrofurane etc.
Owing to the comparatively high speed of reaction the process may easily be carried out continuously. It is also possible to employ the reaction for enhancing the chain length of basic polyamides or polyoxamides of low degree of polymerisation by reacting the same in alcoholic solution with diisocyanates or glycol-bis-chlorocarbonates.
The basic polymers, which are soluble in dilute acetic acid may be cross-linked with diethyloxalate, formaldehyde or compounds yielding formaldehyde upon decomposition, diketenes, diisocyanates, hexahydro-l.3.5-triacrylyl-s-triazine, by which reaction they are rendered insoluble. By suitable selection of the kind and amount of the cross-linking agent products of a varying degree of cross linking, which are more or less capable of swelling, may be obtained.
The products of the invention are suited to a number of industrial applications. Thus, they may be used for rendering textile fibers dyeable with acid dyestufis or water repellent, or they may be employed as binders in pigment printing. For this purpose they are preferably used in the form of their salts in aqueous solution. The solution of the basic polymer in a dilute acid, for instance, acetic acid, is mixed with a pigment paste containing a cross-linking agent and then brought to the necessary thickness by the addition of water and the usual thickener-s. It is possible to adjust the production of the polymers in such a manner that the salts of the polymer yield so viscous an aqueous solution that the addition of a thickener can be omitted. Mixtures of this kind constitute stable printing pastes of favorable consistency. For carrying out the printing, the paste is printed on a surface in the usual manner. In order to start the reaction between the polymer and the cross-linking agent the printed surface is thereupon heated. Prints are obtained which excel by their depth and brilliancy of color, good fastness to rubbing during washing and a very good fastness to boiling in soda. and to light.
It is sometimes of advantage to carry out the production of the basic polymer in the presence of a pigment. The pigmented basic polymers may be employed for pigment printing after dissolving in aqueous acetic acid, adding the cross-linking agent and other suitable auxiliaries. Prints obtained from such polymers possess an especially good fastness to rubbing.
Example 1 wherein 'q is the relative viscosity and c is the concentration in grams per liter.
The polymer is easily'soluble in ethanol and dilute acetic acid and may be cross-linked with cross-ljnking agents, for instance ethyloxalate'and/or cliisocyanates.
Example 2 I .A solution of 167 grams .of -hexamethylene'-.diis'oc y a.
mate in 3 liters of, tertiary butylalcohol is added at C. to the solution of 202 grams of spermin, diaminodipropyltetramethylenediamine of the formula in liters of tertiary butyl alcohol (1 mol hexameth Example 3 An ice-cooled solution of 420 grams of hexamethylenediisocyanate in 5 liters of isobutylalcohol is added to an ice-cooled solution of 51.5 grams of diethylenetriamine and 232 grams of hexamethylenediamine A2 mo1:2 mol) in 6 liters of isobutylalcohol. The polyurea separates turbidly after eight seconds. After ten hours it is sucked off and the polymer dried in vacuo at 80-100 C. Its melting point is 267270 C.,' viscosity number Z17=118 10 3.
Example 4 The alcoholic solutions of 103 grams of diethylenetriamine, 79 grams of pyridine in 4 liters of crude ethanol and 215 grams of tetramethyleneglycol-bis-chlorocarbonate of the formula Cl.CO.O.(CI-I2)4.O.CO.Cl
in 2 liters of crude ethanol are mixed as quickly as possible. After three seconds the solution becomes turbid. A basic polyurethane separates as a hydrochloride; after two hours it is sucked ofi, washed with ethanol and dried at 90100 C. The hydrochloride of the polymer shows a viscosity number of 48 10 in concentrated sulfuric acid and a melting point of 202-204 C. The basic polyurethane may be liberated from the aqueous solution of the hydrochloride by the addition of alkali. It may be cross-linked with the usual crosslinking agents as such or after spinning and cold-drawing and may thus be rendered insoluble.
Example 5 A solution in alcohol of 243 grams of 'hexamethylene- V glycol-bis-chloro-carbonate is dropped within 15 minutes into a cooled solution of 103. grams of diethylenetriamine, 79 grams of pyridine and 5 liters of ethanol. When about 80 per cent of the chlorocarbonate have been dropped in,
the first portions of the basic polyurethane. separate as hydrochloride. .The solution is left to stand for 30 minutes and then the residue sucked oif'and dried in vacuo at 80l00 C. Its viscosity number 2:1 is 70 10 its melting point 203205.5 C.
Example 6 The solution of 0.9 mols of diethyloxalate (131.3 grams in one liter of ethanol) is added to a solution of 1 mol of spermin (202 grams in 5 liters of ethanol). After minutes a freshly prepared solution of 0.1 mol hexamethylenediisocyanate (16.8 grams) in 100 ccs. of alcohol is added. The polymer begins to separate after 5 hours. 24 hours after the addition of the diisocyanate solution the residue is sucked ofif, washed with alcohol and dried in vacuo at 80 C. The yield amounts to 116 grams. The melting point of the polymer is 146148 C., the viscosity number z 45 l0- The polymer dissolves easily in dilute acetic acid.
Example 7 A The solution of 0.1 mol'of hexamethylenediisocyanate (16.8'grams) in 100 ccs. of ethanol are added toa solution of l mol (202 grams) of spermin in 5 liters of ethanol. After 45 minutes a solution of 0.9 mol of diethyloxalate (131 grams) in one liter of ethanol is added. Fivebours. late'rthepolymer. begins tosepariate. It is sucked off after storing for a day, washed with ethanol and dried in vacuo at -90 C. The yield amounts to grams, the melting point is 154-156 C., the viscosity number Z1) is 62 10- 'polyurea amounts to 36.5 kg, of dried polyurea 16.4
kg, which is 96'per cent of the theoretical. The vviscosity number is 400x 10 the melting point 208-2l0 C. The filtrate, which contains low molecular weight compounds may be employed without intermediate distillation as a solvent for the next batches. The yield can thus be increased to 99 per cent of the theoretical. The basic polyurea is easily soluble in dilute acetic, acid and .yields a clear, viscous solution. A 10 per cent solution of its acetate shows a viscosity of 620 centipoise at 25 C.
The basic polyurea can be employed for pigment printing in the following manner:
15 parts by Weight of hexahydro-1.3.5-triacrylyl-s-' triazine 365 parts by weight of water 1000 parts by Weight The mixture described above yields a stable printing paste of good consistence which 'may easily be rinsed with water from the printing rollers or film printing matrices. The printing paste is printed in the usual manner on cotton fabrics or rayon staple fabrics. For aftertreatment the print is predried at 40,70 C.; subsequently prints on cotton are heated to 100-110 C., prints on rayon staple or rayon are heated to 130 C.
The prints on cotton, rayon staple or rayon have good depth and brilliancy of color, very good fastness to rubbing during washing, very good fastness to boiling in soda and to light.
Example 9 'A cooled freshly prepared solution of 171.4 grams 1.02 mol per cent) of hexamethylenediisocyanate in 2.00 ccs. of ethanol is'introduced inside 10 minutes into a cooled solution of 5.05 grams of spermin (2.5 mol per cent), 141.2 grams of 'yl'y-diaminopropylmethylamine (97.5 mol per cent) in two liters of ethanol. After 7 hours the polymer begins to separate; The mixture is stirred for another hour and the basic polyurea precip itated is sucked off, dried for some hours in vacuo at 65-- 70 C. in order to remove the solvent. The yield amounts to 301 grams or 95 per cent or" the theoretical. The melting point is 21l2l3 C., the viscosity number Z11 is 442 10 The basic polyurea easily'dissolves in dilute acetic acid and yields a highly viscous'solution- If under equal conditions 3 mol per cent more of hexamethylenediisocyanate are employed, a polymer of the viscosity number z1 =1557 10 isobtained. This polymer is also still easily soluble in dilute acetic acid but the solutions of its acetate are'fsubstantia lly more viscous than those of thepolyrner having the viscosity number z1 =442 l0 The lO-per' cent solution is so viscous that a glassrod stands therein.
The polyurea thus obtained may be used as a pigment binder in padding according to the following formula:
100 grams of a 10 per cent aqueous solution of the acetate of the basic polyurea are diluted with 10 grams of methylcellulose (70:1000) and 200 grams of water. Thereafter 5 grams of hexamethylenetetramine and 2-4 grams of a pigment paste are added and the whole diluted with water.
After padding the fabric is dried and subsequently heated to 100-120 C. for ten minutes.
Example 10 A cooled freshly prepared solution of 171.4 grams (1.02 mol. per cent) of hexamethylenediisocyanate in ethanol is introduced inside 10 minutes while stirring into a cooled solution of 26.2 grams of dipropylenetriamine (0.2 mol per cent) and 116 grams of -diaminopropyl-methylamine (0.8 mol per cent) in two liters of ethanol. After one hour the basic polyurea formed is sucked off in order to remove the solvent. The polymer is heated in vacuo for some hours to 60-70" C. The yield amounts to 95 per cent of the theoretical. The viscosity number is zn=242 10 the melting point 206- 209 C.
The basic polyurea thus obtained may be employed as a binder in pigment printing according to the following formula:
300 parts by weight of the acetate of the basic polyurea 150 parts by weight of a 20 per cent aqueous red pigment dyestuft paste 20 parts by weight of hexahydro-l.3.5-triacrylyl-striazine 530 parts by weight of Water 1000 parts by weight The after-treatment of the finished print is carried out as in Example 9. The prints are of an even red color and are very fast to light and washing on cotton or rayon staple.
Example 11 The mixture of 135 parts by weight of powdered Hansa Yellow 10 G, 5.06 parts by weight of diethylenetriamine, 135 parts by weight of 'y-y-diaminopropylmethylamine and two liters of ethanol is stirred for two hours at room temperature. The mixture is cooled to -l C. and a freshly prepared cooled solution of 168 parts by weight of hexamethylenediisocyanate in 200 parts by weight of ethanol is dropped in within ten minutes. After stirring for another hour the polymer is sucked ofi and dried for some hours in vacuo at 70 C. The yield amounts to 95 per cent, the viscosity number is zn=860 10- The product dissolves easily in dilute acetic acid and yields a very Viscous solution in which the pigment is extremely finely dissolved. For pigment printing a solution of 5 per cent of the basic polyurea is prepared:
148 grams of the pigmented polyurea are mixed with 22 grams of glacial acetic acid and 1830 grams of water.
400 grams of this solution 100 grams of methylcellulose (:1000) 15 grams of hexahydro-l.3.S-triacrylyl-s-triazine 485 grams of water yield 1000 grams of a printing paste which is printed as described in Example 9. On cotton, rayon staple, or rayon, prints are obtained, which not only have good depth and brilliancy of color, very good fastness to rubbing during washing and a very good fastness to soda and light, but also are extremely fast to rubbing.
We claim:
1. The polyurea of claim 9, in which diethylenetriamine is replaced by dipropylenetriamine.
2. The polyurea of claim 9, in which diethylenetriamine is replaced by diaminodipropyltetramethylene diamine.
3. The process claimed in claim 11, wherein the aliphatic alcohol is ethanol.
4. The process claimed in claim 11, wherein the aliphatic polymethylene diisocyanate is hexamethylenediisocyanate.
5. In the process claimed in claim ll the step which comprises adding a pigment to the reaction mixture.
6. A basic polyurea containing recurring NHCONH CH2) aNH CH2) zNHCONH CH2) 6 groups and being soluble in dilute aqueous acids.
7. A basic polyurea containing recurring groups and being soluble in dilute aqueous acids.
8. A basic polyurea containing recurring groups and being soluble in dilute aqueous acids.
9. A polyurea obtained by reacting in a monohydric lower aliphatic alcohol, a mixture of diethylene triamine and gamma, gamma-diaminopropylmethylamine with about equimolecular proportions of hexamethylene diisocyanate.
10. An aqueous textile printing paste comprising a pigment and as a binder the acetic acid salt of the polymer of claim 9.
11. The process which comprises reacting in a monohydric lower aliphatic alcohol, a diprimary aliphatic diamine containing in its molecule additionally at least one secondary amino group with an aliphatic polymethyl ene diisocyanate.
References Cited in the file of this patent UNITED STATES PATENTS 2,292,443 Hanford Aug. 11, 1942.
2,356,079 Nelles et a1. Aug. 15, 1944 2,660,575 Jones et a1. Nov. 24, 1953 FOREIGN PATENTS 888,938 France Dec. 27, 1943 951,486 France Oct. 26, 1949

Claims (2)

  1. 9. A POLYUREA OBTAINED BY REACTING IN A MONOHYDRIC LOWER ALIPHATIC ALCOHOL, A MIXTURE OF DIETHYLENE TRIAMINE AND GAMMA, GAMMA-DIAMINOPROPYLMETHYLAMINE WITH ABOUT EQUIMOLECULAR PROPORTIONS OF HEXAMETHYLENE DIISOCYANATE.
  2. 10. AN AQUEOUS TEXTILLE PRINTING PASTE COMPRISING A PIGMENT AND AS A BINDER THE ACETIC ACID SALT OF THE POLYMER OF CLAIM 9.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852494A (en) * 1955-01-29 1958-09-16 Bayer Ag Process for the production of polyureas
US3424728A (en) * 1964-02-10 1969-01-28 Toray Industries Aromatic polyquinazolinediones and a process therefor
US3887757A (en) * 1973-05-29 1975-06-03 Inmont Corp Laminates having a polyurethane adhesive
US4157388A (en) * 1977-06-23 1979-06-05 The Miranol Chemical Company, Inc. Hair and fabric conditioning compositions containing polymeric ionenes
US4735984A (en) * 1984-12-25 1988-04-05 Nippon Paint Co., Ltd. Composition containing dispersed pigment and preparation method thereof
US20030212238A1 (en) * 2002-05-10 2003-11-13 Degussa Ag Process for the solvent-free, continuous preparation of polyureas

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2292443A (en) * 1940-07-17 1942-08-11 Du Pont Process for preparing polymeric polyamides
FR888938A (en) * 1941-12-08 1943-12-27 Thueringische Zellwolle Ag Process for the preparation of highly polymerized masses
US2356079A (en) * 1939-03-31 1944-08-15 Gen Aniline & Film Corp Animalizing of cellulosic materials
FR951486A (en) * 1943-05-12 1949-10-26 Ig Farbenindustrie Ag Manufacturing process of linear polymers
US2660575A (en) * 1950-10-02 1953-11-24 Celanese Corp Polymerization process for polyurethanes utilizing water, a water miscible solvent, and a water immiscible solvent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356079A (en) * 1939-03-31 1944-08-15 Gen Aniline & Film Corp Animalizing of cellulosic materials
US2292443A (en) * 1940-07-17 1942-08-11 Du Pont Process for preparing polymeric polyamides
FR888938A (en) * 1941-12-08 1943-12-27 Thueringische Zellwolle Ag Process for the preparation of highly polymerized masses
FR951486A (en) * 1943-05-12 1949-10-26 Ig Farbenindustrie Ag Manufacturing process of linear polymers
US2660575A (en) * 1950-10-02 1953-11-24 Celanese Corp Polymerization process for polyurethanes utilizing water, a water miscible solvent, and a water immiscible solvent

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852494A (en) * 1955-01-29 1958-09-16 Bayer Ag Process for the production of polyureas
US3424728A (en) * 1964-02-10 1969-01-28 Toray Industries Aromatic polyquinazolinediones and a process therefor
US3887757A (en) * 1973-05-29 1975-06-03 Inmont Corp Laminates having a polyurethane adhesive
US4157388A (en) * 1977-06-23 1979-06-05 The Miranol Chemical Company, Inc. Hair and fabric conditioning compositions containing polymeric ionenes
US4735984A (en) * 1984-12-25 1988-04-05 Nippon Paint Co., Ltd. Composition containing dispersed pigment and preparation method thereof
US20030212238A1 (en) * 2002-05-10 2003-11-13 Degussa Ag Process for the solvent-free, continuous preparation of polyureas
US7129313B2 (en) * 2002-05-10 2006-10-31 Degussa Ag Process for the solvent-free, continuous preparation of polyureas

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